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The magnetic orientation was studied for paramagnetic organic radical crystals 1,3,5-triphenyl-6-oxoverdazyl and 1,5-di-p-tolyl-3-phenyl-6-xoverdazyl. The X-ray diffraction measurement revealed that the crystals are oriented with the crystallographic c axis perpendicular to the field.

The development of reusable solid catalysts based on naturally abundant metal elements for the liquid-phase selective oxidation of light alkanes under mild conditions to obtain desired oxygenated products, such as alcohols and carbonyl compounds, remains a challenge. In this study, various perovskite oxide nanoparticles were synthesized by a sol-gel method using aspartic acid, and the effects of A- and B-site metal cations on the liquid-phase oxidation of isobutane to tert -butyl alcohol with molecular oxygen as the sole oxidant were investigated. Iron-based perovskite oxides containing Fe 4+ such as BaFeO 3-δ , SrFeO 3-δ , and La 1- x Sr x FeO 3-δ exhibited catalytic performance superior to those of other Fe 3+ - and Fe 2+ -based iron oxides and Mn-, Ni-, and Co-based perovskite oxides. The partial substitution of Sr for La in LaFeO 3 significantly enhanced the catalytic performance and durability. In particular, the La 0.8 Sr 0.2 FeO 3-δ catalyst could be recovered by simple filtration and reused several times without an obvious loss of its high catalytic performance, whereas the recovered BaFeO 3-δ and SrFeO 3-δ catalysts were almost inactive. La 0.8 Sr 0.2 FeO 3-δ promoted the selective oxidation of isobutane even under mild conditions (60 °C), and the catalytic activity was comparable to that of homogeneous systems, including halogenated metalloporphyrin complexes. On the basis of mechanistic studies, including the effect of Sr substitution in La 1- x Sr x FeO 3-δ on surface redox reactions, the present oxidation proceeds via a radical-mediated oxidation mechanism, and the surface-mixed Fe 3+ /Fe 4+ valence states of La 1- x Sr x FeO 3-δ nanoparticles likely play an important role in promoting C-H activation of isobutane as well as decomposition of tert -butyl hydroperoxide.

We report the synthesis and characterization of tris(biphenyl-2,2'-diyl)metal complexes of trivalent group 9 elements ( 1 , M = Co, Rh, Ir) and their nonplanarly π-extended analogs, tris(1,1'-binaphthyl-2,2'-diyl)metal complexes ( M , M = Rh, Ir). Single crystal X-ray crystallography reveals the distorted octahedral geometry with an approximate 2 M (M = Co, Rh, Ir) and C (M = Rh, Ir), which are contacted by three Li 3 symmetry of trianionic complexes 1 M (M = Co, Rh, Ir) and 2 M (M = Rh, Ir), which are contacted by three Li + ions in the crystal. Complex 1 Ir exhibits yellow luminescence in THF with a photoluminescence quantum yield ( Φ PL ) of up to 0.73, along with a distinctive photophysical property, namely, a concentration dependence of the emission wavelength from 530 to 580 nm. This is a characteristic property of 1 Ir and has not been observed in its isoelectronic analog, tris(2-phenylpyridinato)iridium(III) (Ir(ppy) 3 ). The concentration-dependent optical properties originate from the dissociation equilibria of Li + ions from the anionic chromophore. Complex 2 Ir also exhibits luminescence at 715 nm in THF, with a notable bathochromic shift from 1 Ir through the π-extension. The findings offer insights into the photophysical properties of homoleptic organo-transition metal complexes, providing the foundation for the design of related transition metal complexes.

The development of materials with circularly polarized luminescence (CPL) properties is a promising but challenging frontier in advanced materials science. Modulating the chiral properties of chiral polymers has also been a focus of research. Studies have been conducted to control the ground-state chirality of chiral polymers by adjusting the concentration of the chiral dopant. However, the chirality inversion of CPL of fluorescent liquid crystal particles by chiral dopant concentration has not been reported. Here, we report the preparation of fluorescent cholesteric liquid crystal (FCLC) particles that display polarizable structural color and CPL, demonstrating how varying the chiral dopant amount can reverse the CPL direction, leading to systems where the rotation directions of polarizable structural color and CPL either align or differ. This study confirmed the critical role played by the formation of the twist grain boundary phase in inducing the inversion of the ground-state chirality of FCLC particles and, subsequently, triggering the inversion process of CPL chirality. Furthermore, it leverages chiral structural color and fluorescence of FCLC particles to develop a sophisticated dual verification system. This system, utilizing both circularly polarized light and fluorescence, offers enhanced anticounterfeiting protection for high-value items.

In this paper, we describe the formation of an ordered structure in a copolymer thin film through hydration, which subsequently transitions to a different ordered structure upon dehydration. A statistical copolymer of poly( N -octadecyl acrylamide- stat -hydroxymethyl acrylamide) with a comonomer content ratio of 1:1, denoted as p(ODA50/HEAm50), was synthesized via free radical copolymerization. We prepared a thin film of this copolymer on a solid substrate and annealed it at 60 °C under humid conditions. This treatment formed a side-chain segregated lamellar (SCSegL) structure, in which the ODA and HEAm units are oriented perpendicularly to the polymer backbone and opposite each other. Increasing the annealing temperature to 90 °C led to a transition to a side-chain mixed lamellar (SCMixL) structure, where the ODA and HEAm units are also oriented perpendicularly to the polymer backbone but in both directions. The quartz crystal microbalance (QCM) data indicate that p(ODA50/HEAm50) exhibits LCST-like behavior with a transition temperature of approximately 50 °C. We conclude that the formation of the SCSegL structure at 60 °C is due to pronounced segregation between the water-adsorbed HEAm groups and the hydrophobic ODA. Conversely, dehydration at 90 °C reduces the segregation forces, forming the SCMixL structure, which exhibits lower strain. These results demonstrate that the p(ODA50/HEAm50) film undergoes an order-to-order transition driven by the hydration-dehydration process. Additionally, we found that changes in the lamellar structure significantly alter the swelling properties of the film.

Cobalt (Co) is a promising candidate to replace noble metals in the hydrogenation process, which is widely employed in the chemical industry. Although the catalytic performance for this reaction has been considered to be significantly dependent on the Co crystal phase, no satisfactory systematic studies have been conducted, because it is difficult to synthesize metal nanoparticles that have different crystalline structures with similar sizes. Here we report a new method for the synthesis of cobalt nanoparticles using hydrosilane as a reducing agent (hydrosilane-assisted method). This new method uses 1,3-butanediol and propylene glycol to successfully prepare fcc and hcp cobalt nanoparticles, respectively. These two types of Co nanoparticles have similar sizes and surface areas. The hcp Co nanoparticles exhibit higher catalytic performance than fcc nanoparticles for the hydrogenation of benzonitrile under mild conditions. The present hcp Co catalyst is also effective for highly selective benzyl amine production from benzonitrile without ammonia addition, whereas many catalytic systems require ammonia addition for selective benzyl amine production. Mechanistic studies revealed that the fast formation of the primary amine and the prevention of condensation and secondary amine hydrogenation promote selective benzonitrile hydrogenation for benzylamine over hcp Co nanoparticles.

Chitosan is a product of deacetylated chitin and a natural polymer that is attractive as a functional and biocompatible material in the pursuit of alternative materials to synthetic plastics for a sustainable society. Although hierarchical architectures, from precise molecular structures to nanofibers and twisted structures, have been clarified, the expansion of the anisotropic microstructures of chitosan into millimeter-scale materials is in the process of development. In this study, a chitosan network was reconstructed from an aqueous solution by using the meniscus splitting method to form a three-dimensionally ordered microstructure. A chitosan membrane deposited on the millimeter scale formed a useful anisotropically pH-responsive hydrogel. During the evaporation of the aqueous solution from a finite space, chitosan underwent ordered deposition by capillary force to form a membrane with oriented microstructures and microlayers. Unlike the cast films formed between solid-liquid and air-liquid interfaces, this membrane formed between two air-liquid interfaces. As a result, the membranes with ordered microstructures were capable of signifying directional swelling in aqueous environments and reversible/irreversible swelling-deswelling changes by controlling the pH range. We envision that the anisotropic pH response of the chitosan network can be utilized under physiological conditions as a next-generation material.

Hexagonal boron nitride (hBN) has a property similar to that of graphene, and it has become one of the most popular materials due to its flexible physical and chemical properties for a variety of applications, especially in nanoelectronics. Enhanced properties of hBN-based heterostructures are crucial for future electronic devices. In this work, a sheet-like hBN crystal was synthesized and transferred onto SiO 2 /Si substrate and reduced graphene oxide (RGO)/SiO 2 /Si substrate. Accordingly, the hBN and hBN/RGO films are investigated by optical microscopy, X-ray diffraction, high-resolution transmission electron microscopy, Raman spectroscopy, and atomic force microscopy. The thickness of a single hBN layer is approximately 0.4 nm. A few layers of hBN stacked in large areas are mostly observed in both hBN and the hBN/RGO films. By using Kelvin probe force microscopy, it was found that the hBN/RGO heterostructure has a contact surface potential higher than that of the hBN layer. The large-scale synthesis and fabrication of hBN/RGO films could be extended to fabricate other van der Waals heterostructures., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The density of the side chain introduced to a polymer main chain greatly influences the properties and functions of the polymer. This work first reports on the packing structure and properties at an interface of a poly(substituted methylene) where an azobenzene side chain is introduced at every carbon atom in the main chain (C1PAz). The structure and properties are compared with those of a conventional vinyl polymer [poly(methacrylate)] possessing an identical side-chain structure (C2PAz). The packing structure in the bulk state analyzed by X-ray measurements revealed that C1PAz adopts a highly ordered rectangular unit cell structure, whereas C2PAz shows a less ordered lamellar one. Langmuir film balance experiments indicated that both polymers with the trans -azobenzene give essentially the identical 2D side-chain occupying area on water, which agrees well with the smectic B (hexatic packing) model based on the X-ray data. Upon transfer onto a solid substrate, only C1PAz shows a conformational transformation to a spread bilayer-type layer, most probably due to conformational frustration stemming from the crowding of the side chains. This study proposes new insights into the effects of side-chain density on the self-assembly and photoreaction of azobenzene-containing polymers, which are expected to expand the possibilities of polymer design for various applications.

Metal-organic frameworks (MOFs) are promising materials because of their high designability of pores and functionalities. Especially, MOF thin films and their properties have been investigated toward applications in nanodevices. Typically, MOF thin films are fabricated by using a bottom-up method such as layer-by-layer (LbL) growth in air. Because the water molecules can coordinate and be replaced with organic linkers during synthesis, humidity conditions will be expected to influence the LbL growth processes. In this study, we fabricated MOF thin films composed of Zn 2+ , tetrakis-(4-carboxyphenyl)-porphyrin (TCPP), and 4,4'-bipyridyl (bpy) at 10 and 40% relative humidity (RH) conditions. Then, we investigated the humidity effects on chemical compositions of TCPP and bpy, periodic structure, orientation, and surface morphology. At high RH, coordination replacement of water with the organic linkers becomes more competitive than that at low RH, resulting in a different TCPP/bpy composition ratio between the two RH conditions. Also, more frequent coordination replacements of water with the organic linkers at high RH led to the formation of phases other than that observed at low RH, loss of growth orientation, and rough surface. The findings clarified the importance of controlling the RH condition during LbL growth to obtain the desired coordination networks.

Optically transparent and colored elastomers with high toughness are expected to play an important role in the construction of advanced medical materials, wearable displays, and soft robots. In this study, we found that composite elastomers consisting of amorphous SiO 2 particles homogeneously dispersed in high concentrations within a biocompatible acrylic polymer network exhibit optical transparency and bright structural colors. In the composite elastomers, the system in which the SiO 2 particles form a colloidal amorphous array hardly changes its structural color hue despite deformation due to elongation. Furthermore, the composite elastomer of the SiO 2 particles with the acrylic polymer network also results in high mechanical toughness. In summary, we have shown that the elastomer that exhibits fade-resistant structural coloration formed from safe materials can combine stable coloration and mechanical strength independent of their shape. This is expected to have new potential in future technologies to support our daily life.

The liquid-phase reduction method for the preparation of metal nanoparticles (NPs) by the reduction of metal salts or metal complexes in a solvent with a reducing agent is widely used to prepare Ni NPs that exhibit high catalytic activity in various organic transformations. Intensive research has been conducted on control of the morphology and size of Ni NPs by the addition of polymers and long-chain compounds as protective agents; however, these agents typically cause a decrease in catalytic activity. Here, we report on the preparation of Ni NPs using hydrosilane (Ni-Si) as a reducing agent and a size-controlling agent. The substituents on silicon can control not only the size but also the crystal phase of the Ni NPs. The prepared Ni NPs exhibited high catalytic performance for the hydrogenation of unsaturated compounds, aromatics, and heteroaromatics to give the corresponding hydrogenated products in high yields. The unique feature of Ni catalysts prepared by the hydrosilane-assisted method is that the catalysts can be handled under air as opposed to conventional Ni catalysts such as Raney Ni. Characterization studies indicated that the surface hydroxide was reduced under the catalytic reaction conditions with H 2 at around 100 °C and with the assistance of organosilicon compounds deposited on the catalyst surface. The hydrosilane-assisted method presented here could be applied to the preparation of supported Ni catalysts (Ni-Si/support). The interaction between the Ni NPs and a metal oxide support enabled the direct amination of alcohols with ammonia to afford the primary amine selectively.

Digital enzyme assays are emerging biosensing methods for highly sensitive quantitative analysis of biomolecules with single-molecule detection sensitivity. However, current digital enzyme assays require a fluorogenic substrate for detection, which limits the applicability of this method to certain enzymes. ATPases and kinases are representative enzymes for which fluorogenic substrates are not available; however, these enzymes form large domains and play a central role in biology. In this study, we implemented a fluorogenic cascade reaction in a femtoliter reactor array device to develop a digital bioassay platform for ATPases and kinases. The digital cascade assay enabled quantitative measurement of the single-molecule activity of F 1 -ATPase, the catalytic portion of ATP synthase. We also demonstrated a digital assay for human choline kinase α. Furthermore, we developed a digital cascade assay for ATP-synthesizing enzymes and demonstrated a digital assay for pyruvate kinase. These results show the high versatility of this assay platform. Thus, the digital cascade assay has great potential for the highly sensitive detection and accurate characterization of various ADP- and ATP-producing enzymes, such as kinases, which may serve as disease biomarkers.

To obtain safe, high-performance Li-ion batteries, the development of electrolytes with high impact resistance and high ionic conductivity is important. Ionic conductivity at room temperature has been improved by using poly(ethylene glycol) (PEG) diacrylate (PEGDA) to form three-dimensional (3D) networks and solvated ionic liquids. However, the effects of the molecular weight of PEGDA on ionic conductivities and the relationship between ionic conductivities and network structures of cross-linked polymer electrolytes have not been discussed in detail. In this study, the dependence of the ionic conductivity of photo-cross-linked PEG solid electrolytes on the molecular weight of the PEGDA was evaluated. X-ray scattering (XRS) gave detailed information about the dimensions of 3D networks formed by the photo-cross-linking of PEGDA, and the effects of the network structures on the ionic conductivities were discussed.

The development of effective solid acid-base bifunctional catalysts remains a challenge because of the difficulty associated with designing and controlling their active sites. In the present study, highly pure perovskite oxide nanoparticles with d 0 -transition-metal cations such as Ti 4+ , Zr 4+ , and Nb 5+ as B was increased to 46 m 3 was increased to 46 m 2 g -1 by a simple procedure of changing the atmosphere from N 2 to air during calcination of an amorphous precursor. The resultant SrTiO 3 nanoparticles showed the highest catalytic activity for the cyanosilylation of acetophenone with trimethylsilyl cyanide (TMSCN) among the tested catalysts not subjected to a thermal pretreatment. Various aromatic and aliphatic carbonyl compounds were efficiently converted to the corresponding cyanohydrin silyl ethers in good-to-excellent yields. The present system was applicable to a larger-scale reaction of acetophenone with TMSCN (10 mmol scale), in which 2.06 g of the analytically pure corresponding product was isolated. In this case, the reaction rate was 8.4 mmol g -1 min -1 , which is the highest rate among those reported for heterogeneous catalyst systems that do not involve a pretreatment. Mechanistic studies, including studies of the catalyst effect, Fourier transform infrared spectroscopy, and temperature-programmed desorption measurements using probe molecules such as pyridine, acetophenone, CO 2 , and CHCl 3 , and the poisoning effect of pyridine and acetic acid toward the cyanosilylation, revealed that moderate-strength acid and base sites present in moderate amounts on SrTiO 3 most likely enable SrTiO 3 to act as a bifunctional acid-base solid catalyst through cooperative activation of carbonyl compounds and TMSCN. This bifunctional catalysis through SrTiO 3 resulted in high catalytic performance even without a heat pretreatment, in sharp contrast to the performance of basic MgO and acidic TiO 2 catalysts.

Haber-Bosch process produces ammonia to provide food for over 5 billion people; however, it is currently required to be produced without the use of fossil fuels to reduce global CO 2 emissions by 3% or more. It is indispensable to devise heterogeneous catalysts for the synthesis of ammonia below 100-150 °C to minimize the energy consumption of the process. In this paper, we report metallic iron particles with an electron-donating material as a catalyst for ammonia synthesis. Metallic iron particles combined with a mixture of BaO and BaH 2 species in an appropriate manner could catalyze ammonia synthesis even at 100 °C. The iron catalyst revealed that iron can exhibit a high turnover frequency (∼12 s -1 ), which is over an order of magnitude higher than those of other transition metals used in highly active catalysts for ammonia synthesis. This can be attributed to the intrinsic nature of iron to desorb adsorbed hydrogen atoms as hydrogen molecules at low temperatures.

Fully aromatic sulfonated polyimides with a rigid backbone can form lamellar structures under humidified conditions, thereby facilitating the transmission of protons in ionomers. Herein, we synthesized a new sulfonated semialicyclic oligoimide composed of 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA) and 3,3'-bis-(sulfopropoxy)-4,4'-diaminobiphenyl to investigate the influence of molecular organized structure and proton conductivity with lower molecular weight. The weight-average molecular weight ( M w ) determined by gel permeation chromatography was 9300. Humidity-controlled grazing incidence X-ray scattering revealed that one scattering was observed in the out-of-plane direction and showed that the scattering position shifted to a lower angle as the humidity increased. A loosely packed lamellar structure was formed by lyotropic liquid crystalline properties. Although the ch-pack aggregation of the present oligomer was reduced by substitution to the semialicyclic CPDA from the aromatic backbone, the formation of a distinct organized structure in the oligomeric form was observed because of the linear conformational backbone. This report is the first-time observation of the lamellar structure in such a low-molecular-weight oligoimide thin film. The thin film exhibited a high conductivity of 0.2 (±0.01) S cm -1 under 298 K and 95% relative humidity, which is the highest value compared to the other reported sulfonated polyimide thin films with comparable molecular weight., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The orientation of liquid crystal (LC) molecules is significantly governed by solid interfaces and free surfaces, and a variety of functional materials have been developed using these properties. Although LC materials are already in industrial use, particularly for LC display panels, various studies have been conducted in recent years to better grasp the interface behavior of LC molecules. In this work, we succeeded in in situ observations of induction of higher ordered LC phases at the interface between a side-chain LC azobenzene polymer film with a thickness of ∼400 nm and a low-molecular-mass nematic LC, 4'-pentyl-4-cyanobiphenyl of 35 μm thickness, using small-angle X-ray scattering measurements and polarized optical microscopy. It is revealed that the two different mesogens cooperatively form hybrid higher ordered smectic LC phases probably through weak electron transfer immediately after interfacial contact. The induction process consists of three stages in terms of dynamic structure evolutions. Upon UV irradiation, the hybrid smectic LC structure diminished. This study provides new insights into the behavior of LC molecules near the alignment film on the solid substrate.

The pursuit of a high surface area while maintaining high catalytic performance remains a challenge due to a trade-off relationship between these two features in some cases. In this study, mesoporous todorokite-type manganese oxide (OMS-1) nanoparticles with high specific surface areas were synthesized in one step by a new synthesis approach involving crystallization (i.e., solid-state transformation) of a precursor produced by a redox reaction between MnO 4 - reagents. The use of a low-crystallinity precursor with small particles is essential to achieve this solid-state transformation into OMS-1 nanoparticles. The specific surface area reached up to ca. 250 m 2+ reagents. The use of a low-crystallinity precursor with small particles is essential to achieve this solid-state transformation into OMS-1 nanoparticles. The specific surface area reached up to ca. 250 m 2 , which is much larger than those (13-185 m -1 , which is much larger than those (13-185 m 2 g -1 ) for Mg-OMS-1 synthesized by previously reported methods including multistep synthesis or dissolution/precipitation processes. Despite ultrasmall nanoparticles, a linear correlation between the catalytic reaction rates of OMS-1 and the surface areas was observed without a trade-off relationship between particle size and catalytic performance. These OMS-1 nanoparticles exhibited the highest catalytic activity among the Mn-based catalysts tested for the oxidation of benzyl alcohol and thioanisole with molecular oxygen (O 2 ) as the sole oxidant, including highly active β-MnO 2 nanoparticles. The present OMS-1 nanomaterial could also act as a recyclable heterogeneous catalyst for the aerobic oxidation of various aromatic alcohols and sulfides under mild reaction conditions. The mechanistic studies showed that alcohol oxidation proceeds with oxygen species caused by the solid, and the high surface area of OMS-1 significantly contributes to an enhancement of the catalytic activity for aerobic oxidation.

We report the synthesis of nitrogen-doped graphene oxide, with 5.7-7.0 wt % nitrogen doping, from different sizes of precursor graphite and study its effect on the oxygen evolution reaction (OER) activity of IrO 2 in an acidic medium. The nitrogen-doped supports are expected to have pyridinic, pyrrolic, and graphitic functionalities at different ratios responsible for their improved performance. The N-doped supports and catalysts are synthesized via pyrolysis and the hydrothermal method using natural and synthetic graphite of three different flake sizes and evaluated for their structural and electrochemical characteristics. The average size of IrO 2 nanoparticles deposited on the N-doped supports is independent of the flake size and doping amount of nitrogen. The catalysts show optimum current densities but improved stability with increasing flake sizes of 7, 20, and 125 μm. Our results demonstrate that the selection of the flake size of the doped support is necessary to achieve durable catalysts for the OER in an acidic medium., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Heterogeneously catalyzed aerobic oxidative C-H functionalization under mild conditions is a chemical process to obtain desired oxygenated products directly. Nanosized murdochite-type oxide Mg 6 MnO 8 (Mg 6 MnO 8 -MA) was successfully synthesized by the sol-gel method using malic acid. The specific surface area reached up to 104 m 2 g -1 , which is about 7 times higher than those (2-15 m 2 g -1 ) of Mg 6 MnO 8 synthesized by previously reported methods. Mg 6 MnO 8 -MA exhibited superior catalytic performance to those of other Mn- and Mg-based oxides, including manganese oxides with Mn-O-Mn active sites for the oxidation of fluorene with molecular oxygen (O 2 ) as the sole oxidant under mild conditions (40 °C). The present catalytic system was applicable to the aerobic oxidation of various substrates. The catalyst could be recovered by simple filtration and reused several times without obvious loss of its high catalytic performance. The correlation between the reactivity and the p K a of the substrates, basic properties of catalysts, and kinetic isotope effects suggest a basicity-controlled mechanism of hydrogen atom transfer. The 18 O-labeling experiments, kinetics, and mechanistic studies showed that H abstraction of the hydrocarbon proceeds via a mechanism involving O 2 activation. The structure of Mg 6 MnO 8 consisting of isolated Mn 4+ species located in a basic MgO matrix plays an important role in the present oxidation.

Reductive amination of carbonyls to primary amines is of importance to the synthesis of fine chemicals; however, this reaction with heterogeneous catalysts containing earth-abundant metals under mild conditions remains scarce. Here, we show that the nickel catalyst with mixed oxidation states enables such synthesis of primary amines under low temperature (50 °C) and H 2 pressure (0.9 MPa). The catalyst shows activity in both water and toluene. The high activity likely results from the formation of small (ca. 4.6 nm) partially oxidized nickel nanoparticles (NPs) homogeneously anchored onto the silica and their synergistic effect. Detailed characterizations indicate stabilization of NPs through strong metal support interaction via electron donation from the metal to support. We identify that the support endowed with an amphoteric nature shows better performance. This strategy of making small metal-metal oxide NPs will open an avenue toward the rational development of efficient catalysts that would allow for other organic transformations under mild reaction conditions.

We demonstrate that the Halorhodospira halophila (Hhal) photoactive yellow protein (PYP) is not representative of the greater PYP family. The photodynamics of the PYP isolated from Salinibacter ruber (Srub) is characterized with a comprehensive range of spectroscopic techniques including ultrafast transient absorption, photostationary light titrations, Fourier transform infrared, and cryokinetics spectroscopies. We demonstrate that the dark-adapted pG state consists of two subpopulations differing in the protonation state of the chromophore and that both are photoactive, with the protonated species undergoing excited-state proton transfer. However, the primary I 0 photoproduct observed in the Hhal PYP photocycle is absent in the Srub PYP photodynamics, which indicates that this intermediate, while important in Hhal photodynamics, is not a critical intermediate in initiating all PYP photocycles. The excited-state lifetime of Srub PYP is the longest of any PYP resolved to date (∼30 ps), which we ascribe to the more constrained chromophore binding pocket of Srub PYP and the absence of the critical Arg52 residue found in Hhal PYP. The final stage of the Srub PYP photocycle involves the slowest known thermal dark reversion of a PYP (∼40 min vs 350 ms in Hhal PYP). This property allowed the characterization of a pH-dependent equilibrium between the light-adapted pB state with a protonated cis chromophore and a newly resolved pG' intermediate with a deprotonated cis chromophore and pG-like protein conformation. This result demonstates that protein conformational changes and chromophore deprotonation precede chromophore reisomerization during the thermal recovery of the PYP photocycle.

Herein, we present the first study on the polyaddition reaction of biscarbodiimides with chiral diamines, which focuses on a definite case using optically active trans -4a,8a-decahydroquinoxaline and 1,4-phenylenebis(arylcarbodiimide)s, which readily react with each other under ambient and catalyst-free conditions. The specific reactivity allows for facile access to not only the corresponding chiral polyguanidines under balanced stoichiometry but also their oligomeric analogues under imbalanced stoichiometry via a step-by-step procedure. Spectroscopic, chromatographic, and computational characterization of the novel molecular chains containing arrayed guanidines have revealed their structural, optical, and conformational properties as well as the mechanism of polymerization assisted by molecular association. Their potential use as asymmetric catalysts is also described., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Active metal catalysts are the key in chemical industry for sustainable production of multitude of chemical resources. Here, we report a new ruthenium (Ru) composite with a synergistically controlled nanostructure and electronic properties as a highly efficient hydrogenation catalyst which comprises stable small Ru nanoparticles (mean particle size, ca. 0.9 nm) in situ generated into a nanoporous N-functionalized carbon with high surface area ( ca. 650 m 2 g -1 ) and has strong electron-donating power of Ru sites of nanoparticles. The scalable and highly reusable catalyst, prepared from a self-assembled Ru complex, performs actively with low per metal usage under mild conditions (60-80 °C and 0.5-1.0 MPa H 2 ) for selective hydrogenation of various quinolines and pyridines. The role of electron-donating properties of the new Ru nanohybrid for highly efficient catalysis was characterized by both experiments and computational studies. Density functional theory calculations reveal that weak adsorption energies of quinoline at the electron-rich Ru surface prevents poisoning caused by its strong coordination and provides excellent reusability of the catalyst, while low activation barriers for the hydrogenation steps of the N-heterocyclic ring correlate with high catalytic activity. Our catalyst exhibits 5-24-fold higher turnover frequency up to ca. 167 h -1 among the efficient noble metal catalysts reported for selective hydrogenation of quinoline to 1,2,3,4-tetrahydroquinoline.

Mesoporous β-MnO 2 nanoparticles were synthesized by a template-free low-temperature crystallization of Mn 4+ precursors (low-crystallinity layer-type Mn 4+ oxide, c -distorted H + -birnessite) produced by the reaction of MnO 4 - and Mn 2+ . The Mn starting materials, pH of the reaction solution, and calcination temperatures significantly affect the crystal structure, surface area, porous structure, and morphology of the manganese oxides formed. The pH conditions during the precipitation of Mn 4+ precursors are important for controlling the morphology and porous structure of β-MnO 2 . Nonrigid aggregates of platelike particles with slitlike pores ( β - MnO 2 - 1 and - 2 ) were obtained from the combinations of NaMnO 4 /MnSO 4 and NaMnO 4 /Mn(NO 3 ) 2 , respectively. On the other hand, spherelike particles with ink-bottle shaped pores ( β - MnO 2 - 3 ) were formed in NaMnO 4 /Mn(OAc) 2 with pH adjustment (pH 0.8). The specific surface areas for β - MnO 2 - 1 , - 2 , and - 3 were much higher than those for nonporous β-MnO 2 nanorods synthesized using a typical hydrothermal method ( β - MnO 2 - HT ). On the other hand, c -distorted H + -birnessite precursors with a high interlayer metal cation (Na + and K + ) content led to the formation of α-MnO 2 with a 2 × 2 tunnel structure. These mesoporous β-MnO 2 materials acted as effective heterogeneous catalysts for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) as a bioplastic monomer and for the transformation of aromatic alcohols to the corresponding aldehydes, where the catalytic activities of β - MnO 2 - 1 , - 2 , and - 3 were approximately 1 order of magnitude higher than that of β - MnO 2 - HT . β - MnO 2 - 3 exhibited higher catalytic activity (especially for larger molecules) than the other β-MnO 2 materials, and this is likely attributed to the nanometer-sized spaces.

Cellulose paper has strong potential as an analytical platform owing to its unique characteristics. In the present study, we investigated a procedure for functionalizing the surface of cellulose paper by dip-coating a mixture of a functional polymer and a perfluoroalkylated surfactant (surfactant 1). The functional polymer comprised a mixture of methyl methacrylate and poly(ethylene glycol) methacrylate monomers. The monomer ratio in the functional polymer affected the hydrophilicity and water absorbance of the cellulose paper after dip-coating. Furthermore, the presence of surfactant 1 during dip-coating promoted the surface segregation of poly(ethylene glycol) (PEG) moieties in the polymer, which enhanced the hydrophilicity, prevented nonspecific protein adsorption, and maintained the water absorbance of the dip-coated cellulose paper. Dip-coating with another functional polymer containing biotin groups produced a cellulose paper with a biotin-decorated surface in a one-step procedure. The displayed biotin groups immobilized avidin on the surface, and the PEG moieties in the polymer prevented nonspecific protein adsorption. We then immobilized a thrombin-binding DNA aptamer on the avidin-immobilized cellulose paper to prepare a paper-based analytical device. It is possible to visualize thrombin in model solutions and serum using the paper-based analytical device.

Domino 1,4- and 1,6-addition reactions of ketene silyl acetals to dialkynyl imines are disclosed. Aluminum chloride promoted domino 1,4- and 1,6-addition reactions of ketene silyl acetals to dialkynyl imines to give a variety of alkenyl iminocyclobutenones in moderate to good yields. The chemoselective reduction of alkenyl iminocyclobutenones and the subsequent thermal rearrangement of resulting alkenyl aminocyclobutenones in the presence of appropriate amines provided cis or trans multifunctionalized β-lactams in moderate to high yields with good to high diastereoselectivities.

Phosphomolybdates with different P species exhibiting a 1D molecular structure are synthesized. The materials are constructed by a {[Mo VI 6 O 21 ] 6- } n molecular tube as a shell with trapping a redox-active species P in the center. The building units ([(HP III O 3 )Mo VI 6 O 18 ] 2- or [(P V 2 O 7 )Mo VI 12 O 36 ] 4- ) form at room temperature, which further polymerize linearly along the c -axis. Interestingly, the material shows an unusual heat-triggered intramolecular redox property, which undergoes an electron-transfer-oxygen-transfer procedure from [{(HP III O 3 )Mo VI 6 O 18 ] 2- } n to {[(P V 2 O 7 )Mo VI 12 O 36 ] 4- } n /2 . The crystal structure of the material is stable during the oxidation reaction, while the central P is oxidized and the local structure changes.

The understanding of polymer dewetting on solid surfaces is significant in both fundamental polymer physics and practical film technologies. When liquid crystalline (LC) polymers are dewetted, LC ordering is involved in the dewetting process. Here, we report on the characteristic dewetting processes of a diblock copolymer composed of a cyanobiphenyl side chain liquid crystalline polymer (SCLCP) block connected with polystyrene (PS) taking place on a PS base film. Thin films of the block copolymer were prepared by the water-floating method onto the PS film, and the dewetting process is observed in a softened state above the glass transition temperature of the PS. At the smectic A phase temperature of the SCLCP block, the dewetted surface layer generated a flat unique fingering pattern leading to a monolayered (two-dimensional) high-density LC polymer brush through the LC ordering. The important role of the anchoring PS block on the base PS film surface is suggested for the formation of highly stretched LC polymer brush. Above the isotropization temperature, in contrast, ordinary three-dimensional droplet morphologies with smooth round edges were observed. By photo-cross-linking the base PS film, the lateral diffusion rate was significantly reduced. This can be applied to an entropy-driven morphology patterning via dewetting. The polymer brush formation and its spatial controls are expected to provide new opportunities for the modification strategies of polymer surfaces.

When a small-molecule ionic crystal is group-substituted with polymer chain-segments to form an ionomer, do its constrained ionic aggregates maintain ordered internal structures? This work presents, for a Na-salt sulfonated-polystyrene ionomer, reconciled TEM electron-diffraction schlieren textures and WAXS Bragg-type reflections from the ionic-aggregate nanodomains, which solidly prove the aggregates' internal (mono)crystalline order. The observed DSC endotherm of the ionomer, identified by WAXS as an order-disorder transition interior to its aggregates, gradually becomes enhanced over a 3-month, room-temperature physical aging process, indicating that the aggregates' ordering is a slow relaxation process in which the degree of order increases with time. This work corroborates an uncommon form of order, i.e., polymer-bound small-molecule ionic (quasi)crystal, which is supplementary to the order phenomena in small molecules, polymers, and liquid crystals.

The design and development of zeolitic transition metal oxides for selective oxidation are interesting due to the combination of the redox properties and microporosities. Redox-active zeolitic transition metal oxides based on ε-Keggin iron molybdates were synthesized. O 2 can be activated by the materials via an electron-transfer-based process, and the materials can be oxidized even at room temperature. The materials are oxidized and reduced reversibly while the crystal structures are maintained. V is uniformly incorporated in the materials without changing the basic structures, and the redox properties of the materials are tuned by V. The materials are used as robust catalysts for ethyl lactate oxidation to form ethyl pyruvate using O 2 as an oxidant.

Aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) as a bioplastics monomer is efficiently promoted by a simple system based on a nonprecious-metal catalyst of MnO 2 and NaHCO 3 . Kinetic studies indicate that the oxidation of 5-formyl-2-furancarboxylic acid (FFCA) to FDCA is the slowest step for the aerobic oxidation of HMF to FDCA over activated MnO 2 . We demonstrate through combined computational and experimental studies that HMF oxidation to FDCA is largely dependent on the MnO 2 crystal structure. Density functional theory (DFT) calculations reveal that vacancy formation energies at the planar oxygen sites in α- and γ-MnO 2 are higher than those at the bent oxygen sites. β- and λ-MnO 2 consist of only planar and bent oxygen sites, respectively, with lower vacancy formation energies. Consequently, β- and λ-MnO 2 are likely to be good candidates as oxidation catalysts. On the other hand, experimental studies reveal that the reaction rates per surface area for the slowest step (FFCA oxidation to FDCA) decrease in the order of β-MnO 2 > λ-MnO 2 > γ-MnO 2 ≈ α-MnO 2 > δ-MnO 2 > ε-MnO 2 ; the catalytic activity of β-MnO 2 exceeds that of the previously reported activated MnO 2 by three times. The order is in good agreement not only with the DFT calculation results, but also with the reduction rates per surface area determined by the H 2 -temperature-programmed reduction measurements for MnO 2 catalysts. The successful synthesis of high-surface-area β-MnO 2 significantly improves the catalytic activity for the aerobic oxidation of HMF to FDCA.

A rhombohedral BaRuO 3 nanoperovskite, which was synthesized by the sol-gel method using malic acid, could act as an efficient heterogeneous catalyst for the selective oxidation of various aromatic and aliphatic sulfides with molecular oxygen as the sole oxidant. BaRuO 3 showed much higher catalytic activities than other catalysts, including ruthenium-based perovskite oxides, under mild reaction conditions. The catalyst could be recovered by simple filtration and reused several times without obvious loss of its high catalytic performance. The catalyst effect, 18 O-labeling experiments, and kinetic and mechanistic studies showed that substrate oxidation proceeds with oxygen species caused by the solid. The crystal structure of ruthenium-based oxides is crucial to control the nature of the oxygen atoms and significantly affects their oxygen transfer reactivity. Density functional theory calculations revealed that the face-sharing octahedra in BaRuO 3 likely are possible active sites in the present oxidation in sharp contrast to the corner-sharing octahedra in SrRuO 3 , CaRuO 3 , and RuO 2 . The superior oxygen transfer ability of BaRuO 3 is also applicable to the quantitative conversion of dibenzothiophene into the corresponding sulfone and gram-scale oxidation of 4-methoxy thioanisole, in which 1.20 g (71% yield) of the analytically pure sulfoxide could be isolated.

The structural determination of nanomaterials and their application in energy storage and transfer are of great importance. Herein, a layered zirconomolybdate with a two-dimensional structure was synthesized. Atomic resolution electron microscopy was utilized for direct visualization of the structure that was further confirmed by powder X-ray diffraction and X-ray absorption near-edge structure analyses. The structure of the molecular sheet was stable at a high temperature in an oxidative atmosphere. The electrochemical performance of the material was evaluated with a Li battery composed of the calcined material as a cathode. Li ions were reversibly inserted and extracted between the layers without collapse of the structure of the material. The electrochemical properties of the material were derived from the reversible redox activity of the Mo ions and Zr ions in the material as well as the flexibility of the molecular layer of the material.

Aromaticity of photoexcited molecules is an important concept in organic chemistry. Its theory, Baird's rule for triplet aromaticity since 1972 gives the rationale of photoinduced conformational changes and photochemical reactivities of cyclic π-conjugated systems. However, it is still challenging to monitor the dynamic structural change induced by the excited-state aromaticity, particularly in condensed materials. Here we report direct structural observation of a molecular motion and a subsequent packing deformation accompanied by the excited-state aromaticity. Photoactive liquid crystal (LC) molecules featuring a π-expanded cyclooctatetraene core unit are orientationally ordered but loosely packed in a columnar LC phase, and therefore a photoinduced conformational planarization by the excited-state aromaticity has been successfully observed by time-resolved electron diffractometry and vibrational spectroscopy. The structural change took place in the vicinity of excited molecules, producing a twisted stacking structure. A nanoscale torque driven by the excited-state aromaticity can be used as the working mechanism of new photoresponsive materials.

Highly selective synthesis of primary amines over heterogeneous catalysts is still a challenge for the chemical industry. Ruthenium nanoparticles supported on Nb 2 O 5 act as a highly selective and reusable heterogeneous catalyst for the low-temperature reductive amination of various carbonyl compounds that contain reduction-sensitive functional groups such as heterocycles and halogens with NH 3 and H 2 and prevent the formation of secondary amines and undesired hydrogenated byproducts. The selective catalysis of these materials is likely attributable to the weak electron-donating capability of Ru particles on the Nb 2 O 5 surface. The combination of this catalyst and homogeneous Ru systems was used to synthesize 2,5-bis(aminomethyl)furan, a monomer for aramid production, from 5-(hydroxymethyl)furfural without a complex mixture of imine byproducts.

A simple and efficient synthetic method for preparing high-surface-area perovskites was investigated by focusing on the importance of the formation of an amorphous precursor. Hexagonal SrMnO 3 with high surface area was successfully synthesized by simple calcination of the amorphous precursor prepared using aspartic acid and metal acetates instead of metal nitrates , without pH adjustment. The specific surface area reached up to ca. 50 m 2 g -1 , which is much larger than that for SrMnO 3 synthesized by previously reported methods. The catalytic activity for heterogeneous liquid-phase aerobic oxidation was significantly improved in comparison with the polymerized complex method, and the present catalytic system was applicable to the oxidation of various substrates., Competing Interests: The authors declare no competing financial interest.

The photoactive yellow protein (PYP) from Halorhodospira halophila (Hhal) is a bacterial photoreceptor and model system for exploring functional protein dynamics. We report ultrafast spectroscopy experiments that probe photocycle initiation dynamics in the PYP domain from the multidomain PYP-phytochrome-related photoreceptor from Rhodospirillum centenum (Rcen). As with Hhal PYP, Rcen PYP exhibits similar excited-state dynamics; in contrast, Rcen PYP exhibits altered photoproduct ground-state dynamics in which the primary I 0 intermediate as observed in Hhal PYP is absent. This property is attributed to a tighter, more sterically constrained binding pocket around the p-coumaric acid chromophore due to a change in the Rcen PYP protein structure that places Phe98 instead of Met100 in contact with the chromophore. Hence, the I 0 state is not a necessary step for the initiation of productive PYP photocycles and the ubiquitously studied Hhal PYP may not be representative of the broader PYP family of photodynamics.

Anion conductivity at the surfaces of two anion-exchange membranes (AEMs), quaternized ammonium poly(arylene ether) multiblock copolymer (QPE-bl-3) and quaternized ammonium poly(arylene perfluoro-alkylene) copolymer (QPAF-1), synthesized by our group was investigated using current-sensing atomic force microscopy under purified air at various relative humidities. The anion-conducting spots were distributed inhomogeneously on the surface of QPE-bl-3, and the total areas of the anion-conducting spots and the current at each spot increased with humidity. The anion-conductive areas on QPAF-1 were found on the entire surface even at a low humidity. Distribution of the anion-conducting spots on the membrane was found to directly affect the performance of an AEM fuel cell.

Size-controlled metal nanoparticles (NPs) were spontaneously formed when the amphiphilic diblock copolymers consisting of poly(vinyl catechol) and polystyrene (PVCa-b-PSt) were used as reductants and templates for NPs. In the present study, the proton conductivity of well-aligned lamellae structured PVCa-b-PSt films with Ag NPs was evaluated. We found that the proton conductivity of PVCa-b-PSt film was increased 10-fold by the addition of Ag NPs into the proton conduction channels filled with catechol moieties. In addition, the effect of humidity and the origin of proton conductivity enhancement was investigated.

The growth of metal-organic coordination network thin films on surfaces has been pursued extensively and intensively to manipulate the molecular arrangement. For this study, the oriented multilayer thin films based on porphyrinic nanoarchitecture were synthesized toward metal-organic coordination networks using surface-induced assembly (SIA). Nanoscale molecular thin films were prepared at room temperature using cobalt(II) ion and porphyrin building blocks as precursors. Stepwise growth with a highly uniform layer was characterized using UV-vis, AFM, IR, and XPS studies. The grazing incidence small-angle X-ray scattering and X-ray reflectivity results remarkably suggested a periodic structure in in-plane direction with constant and high mass density (ca. 1.5 g/cm(3)) throughout the multilayer formation. We propose that orientation of the porphyrin macrocycle plane with a hexagonal packed model by single anchoring mode was tilted approximately 60° with respect to the surface substrate. It is noteworthy that the well-organized structure of porphyrin-based macrocyclic framework on the amine-terminated surface substrate can be achieved efficiently using a simple SIA approach under mild synthetic conditions. The synthesized thin film provides a different structure from that obtained using bulk synthesis. This result suggests that the SIA technique can control not only the film thickness but also the structural arrangement on the surface. This report of our research provides insight into the ordered porphyrin-based metal-organic coordination network thin films, which opens up opportunities for exploration of unique thin film materials for diverse applications.